Abstract
AbstractThe synthesis, structure and aqueous solution behavior of [FeL1Cl2] (1, L1 = 1‐benzyl‐4‐acetato‐1,4,7‐triazacyclononane) is reported. The X‐ray structure of 1 reveals iron(III) in distorted octahedral geometry bonded to three amine nitrogen atoms and one carboxylate oxygen atom along with two cis chloride atoms. Electrochemical measurements of 1 in acetonitrile indicate that E1/2 = −200 mV vs Ag/AgCl. The stability of the +3 oxidation state is attributed to the hard Namine and carboxylate ligand donors. In acetonitrile, 1 is mononuclear and has an S = 5/2 spin state. The presence of a μ‐oxo bridge upon dissolution of 1 in water is supported by EPR and solution magnetic susceptibility NMR studies. pH‐metric titrations and UV‐vis studies indicate the presence of a total of four acidic protons. At low pH, L1(OH2)Fe‐O‐Fe(OH2)L1 is proposed to be stabilized while at high pH, L1(OH)Fe‐O‐Fe(OH)L1 is suggested to persist.
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